Homogenous and heterogenous catalytic activity of metallophthalocyanines towards electrochemical detection of organic compounds

Mafatle, Tsukutlane J.P. (1998) Homogenous and heterogenous catalytic activity of metallophthalocyanines towards electrochemical detection of organic compounds. Masters thesis, Rhodes University.




Cysteine plays an important role in many biological and pharmaceutical systems. Therefore, in view of its importance, it is essential to find means of detecting it at the lowest possible levels. In this regard, electrochemical techniques have been found to be capable of detecting analytes even at micro levels. However, electrochemical determination of cysteine occurs at a very high potentials. These overpotentials makes quantitative analysis or detection of cysteine difficult at most conventional carbon electrodes. On platinum electrode, the oxidation of cysteine has been reported to occur in the potential range 0.7 to 1.45 V (vs NHE). Therefore, the object of this investigative study has been to find an active complex that could replace platinum and other expensive metals as electrodes. Such a complex should also be capable of reducing the potential at which the oxidation of cysteine occurs on carbon electrodes. As a result, this manuscript gives a full report on the investigative study of electrocatalytic activity of molybdenum phthalocyanine complexes towards detection of cysteine. Molybdenum phthalocyanine, OMo(OH)Pc, and its tetrasulfonated derivative, [OMo(OH)TSPc]⁴⁻ were successfully used to reduce the potential needed to initiate the oxidation of cysteine on carbon paste electrodes (CPE). The oxidation of cysteine on CPE modified with [OMo(OH)Pc]⁴⁻ was found to occur at 0.29 V (vs AgIAgCl), and in the presence of [OMo(OH)TSPc]⁴⁻ species in solution the oxidation occurred at 0.33 V (vs AgIAgCl). Molybdenum, in the oxidation states of Mo(IV), Mo(V) and Mo(VI), is found in biological systems as an essential trace element, participating in a number of enzymatic reactions, where it is believed to be coordinated to sulphur-containing ligands in many molybdenum enzymes. This therefore explains why molybdenum phthalocyanines were employed in electroanalytical detection of sulphur containing amino acid, cysteine. Electrochemical methods have also been successfully used in detection of environmental pollutants such as phenolic compounds. Phenolic compounds are oxidised at readily accessible potentials. However, like cysteine, there are problems associated with the electrochemical detection of these important environmental pollutants. Their electrooxidation is known to form dimeric and/or polymeric oxidation products which adsorb onto the electrode surface, thus -videactivating it. Therefore, to address this problem, cobalt phthalocyanine (CoPc) and its tetrasulfonated derivative, [CoTSPc]⁴⁻ were employed in electrocatalytic detection of phenolic compounds. These complexes were found to increase the anodic peak currents for the oxidation of o-cresol, m-cresol, p-cresol, phenol, 2-chlorophenol and 4-chlorophenol. In addition, CoPc deposited onto the glassy carbon electrode improved the stability of the electrode, by reducing electrode poisoning caused by the electrooxidation products of the mentioned phenolic compounds. The potential at which the oxidation occurred and the current response of individual phenolic compounds depended on the degree of substitution and the type of substituent on the phenol molecule. In general, the current response was found to be lower for chlorinated phenols compared with the cresols and phenol. To establish the role of the central metal in the catalytic process, comparison of the electrocatalytic activity of some of the first row transition metal phthalocyanines, for the detection of mono-substituted phenolic compounds, showed the following trend: Co⁽¹¹⁾ > Mn⁽¹¹⁾ > Fe⁽¹¹⁾Pc > Ni⁽¹¹⁾Pc > Cu⁽¹¹⁾Pc > H₂Pc > Zn⁽¹¹⁾Pc > Bare GCE. A report is also given on electrocatalysis using [CoTSPc]⁴⁻ electrochemically deposited on the glassy carbon electrode. This was also found to enhance the anodic peak currents for the oxidation of all phenolic compounds. A report on the effects of scan rate, operating potential, analyte concentration and other variables is also given.

Item Type:Thesis (Masters)
Uncontrolled Keywords:Cysteine, Biological systems, Pharmaceutical systems, Detection, Electrochemical techniques, Analytes, Quantitative analysis, Carbon electrodes, Active complex, Platinum, Molybdenum phthalocyanine complexes, Oxydation, Enzymatic reactions, Sulphur, Ligands, Amino acid, Pollutants, Phenolic compounds, Anodic peak currents
Subjects:Q Science > QD Chemistry
Q Science > QD Chemistry > QD71 Analytical chemistry
Divisions:Faculty > Faculty of Science > Chemistry
Supervisors:Nyokong, T.
ID Code:3036
Deposited By: Philip Clarke
Deposited On:26 Jun 2012 10:22
Last Modified:26 Jun 2012 10:22
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